Epoxy reactive diluent, preparation method and application thereof, and epoxy resin material

Abstract

The invention belongs to the technical field of organic synthesis, and provides an epoxy reactive diluent, a preparation method and application thereof, and an epoxy resin material. The epoxy reactive diluent provided by the invention comprises the following preparation raw materials: alcohol substances (comprising one or more of fatty alcohol and ether alcohol substances), methyl epichlorohydrin, inorganic base and a phase transfer catalyst. The number of carbon atoms of the alcohol substance is 1-14. The epoxy reactive diluent is prepared by taking the alcohol substance and the methyl epichlorohydrin as raw materials, and when the obtained epoxy reactive diluent is used for diluting epoxy resin, the epoxy reactive diluent not only has the effects of dilution and viscosity reduction, but also can improve the mechanical properties (tensile strength, elongation at break, bending strength and impact strength) of the obtained epoxy resin material. Besides, the variety of the epoxy reactive diluent is expanded, and due to the existence of the methyl branched chain, the synthesized epoxy reactive diluent is high in boiling point, and in the using process, the volatilization loss is small, the irritation to human skin is small, and the atmospheric pollution is small.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to an epoxy reactive diluent, a preparation method and application thereof, and an epoxy resin material. Background Art

[0002] Epoxy resin has excellent bonding properties, mechanical strength, good electrical insulation and chemical stability, and has been widely used in adhesives, electronics and electrical, and automobile manufacturing. However, due to the shortcomings of bisphenol A epoxy resin after curing, such as high crosslinking density, high brittleness, flammability and high viscosity, it is difficult to meet the process requirements for manufacturing advanced composite materials, which seriously limits the application of epoxy resin in many important fields. Therefore, adding a certain amount of diluent to the epoxy resin system is an important way to improve the operation process and application performance of epoxy resin. In the curing process, the inactive diluent of epoxy resin does not participate in the chemical reaction of the system and can only escape in the form of gas, which will not only cause voids in the resin cured product, increase the shrinkage rate, reduce the bonding force, mechanical strength and heat deformation temperature, but also cause the VOCs discharged to pollute the environment. However, due to the presence of epoxy groups in the structure, the epoxy active diluent not only does not produce volatiles during the curing process, but is also environmentally friendly, and can also dilute the epoxy resin and improve the flexibility of the cured product, effectively improving the operating conditions and product performance.

[0003] In the prior art, epoxy resin reactive diluents are all prepared using epichlorohydrin as a raw material. Although the epoxy resin reactive diluents prepared using epichlorohydrin as a raw material can improve the mechanical properties of the epoxy resin, the degree of improvement in the mechanical properties is limited. Summary of the invention

[0004] In view of this, the purpose of the present invention is to provide an epoxy reactive diluent and its preparation method and application, and epoxy resin material. When the epoxy reactive diluent provided by the present invention is used as a diluent to dilute epoxy resin, it not only has the effect of diluting and reducing viscosity, but also can improve the mechanical properties of the obtained epoxy resin material.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] An epoxy reactive diluent comprises the following preparation raw materials:

[0007] Alcohols, methyl epichlorohydrin, inorganic bases and phase transfer catalysts;

[0008] The alcohol substance has 1 to 14 carbon atoms;

[0009] The alcohol substance includes one or more of fatty alcohol and ether alcohol substances.

[0010] Preferably, the fatty alcohol includes one or more of fatty monohydric alcohol, fatty dihydric alcohol, fatty trihydric alcohol and fatty tetrahydric alcohol;

[0011] The fatty monohydric alcohol includes one or more of methanol, ethanol, propanol, butanol, octanol, decanol, undecanol, dodecanol, tridecanol and tetradecanol;

[0012] The fatty diol includes one or more of ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol and neopentyl glycol;

[0013] The fatty triol includes trimethylolpropane;

[0014] The fatty tetraol includes pentaerythritol;

[0015] The ether alcohol substances include diethylene glycol and / or dipropylene glycol.

[0016] Preferably, the phase transfer catalyst is a quaternary ammonium salt; the quaternary ammonium salt includes one or more of benzyltriethylammonium chloride, benzyltrimethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride and dodecyldimethyl dipolyglycerol ether ammonium chloride.

[0017] Preferably, the inorganic base comprises sodium hydroxide.

[0018] Preferably, the ratio of the amount of the alcohol substance to the amount of methyl epichlorohydrin is 1:1 to 40;

[0019] The ratio of the total mass of the alcohol substance and methyl epichlorohydrin to the mass of the phase transfer catalyst is 100:0.01-10;

[0020] The molar ratio of the alcohol substance to the inorganic base is 1:1-10.

[0021] The present invention also provides a method for preparing the epoxy reactive diluent described in the above technical solution, comprising the following steps:

[0022] The alcohol substance, methyl epichlorohydrin, an inorganic base and a phase transfer catalyst are mixed and reacted to obtain the epoxy active diluent.

[0023] Preferably, the reaction temperature is 20-100° C., and the insulation time is 1-24 h.

[0024] The present invention also provides the use of the epoxy reactive diluent described in the above technical solution or the epoxy reactive diluent prepared by the preparation method described in the above technical solution in epoxy resin materials.

[0025] The present invention also provides an epoxy resin material, comprising the following preparation raw materials: epoxy resin, active diluent and curing agent;

[0026] The active diluent is the epoxy active diluent described in the above technical solution or the epoxy active diluent prepared by the preparation method described in the above technical solution.

[0027] Preferably, the amount of the epoxy reactive diluent added is 5 to 20% of the mass of the epoxy resin;

[0028] The epoxy resin includes bisphenol A epoxy resin;

[0029] The curing agent includes diethylenetriamine.

[0030] The invention provides an epoxy reactive diluent.

[0031] The present invention uses alcohol substances and methyl epichlorohydrin as raw materials to prepare epoxy reactive diluents. When the obtained epoxy reactive diluent is used to dilute epoxy resin, it not only has dilution and viscosity reduction effects, but also can improve the mechanical properties of the obtained epoxy resin material, including tensile strength, elongation at break, bending strength and impact strength. In addition, the present invention expands the variety of epoxy reactive diluents; and due to the presence of methyl side chains, the synthesized epoxy reactive diluent has a higher boiling point, and during use, the volatilization loss is small, the irritation to human skin is small, and the air pollution is small. In addition, methyl epichlorohydrin has good insulation performance, chemical corrosion resistance and thermal resistance performance. When the epoxy reactive diluent prepared by using it as a raw material is used to prepare epoxy resin materials, the insulation, chemical corrosion resistance and thermal resistance of the obtained epoxy resin materials can be improved.

[0032] Furthermore, methyl epichlorohydrin is a byproduct of industrial production of isobutylene. Methyl epichlorohydrin is a byproduct of industrial production of isobutylene with abundant output. The present invention uses methyl epichlorohydrin as a raw material to prepare epoxy reactive diluent, solves the problem of excess methyl epichlorohydrin as an industrial byproduct, and realizes high added value of the byproduct methyl epichlorohydrin. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 This is the infrared spectrum of neopentyl glycol di(β-methyl)glycidyl ether prepared in Example 3;

[0034] Figure 2 This is a graph showing the effect of different addition amounts of neopentyl glycol di(β-methyl)glycidyl ether prepared in Example 3 on the viscosity reduction effect of epoxy resin. DETAILED DESCRIPTION

[0035] The present invention provides an epoxy reactive diluent, comprising the following preparation raw materials:

[0036] Alcohols, methyl epichlorohydrin, inorganic bases and phase transfer catalysts;

[0037] The alcohol substance has 1 to 14 carbon atoms;

[0038] The alcohol substance includes one or more of fatty alcohol and ether alcohol substances.

[0039] The raw materials for preparing the epoxy reactive diluent provided by the present invention include alcohol substances, and the number of carbon atoms of the alcohol substances is 1 to 14. In the present invention, the alcohol substances include one or more of fatty alcohols and ether alcohol substances. In the present invention, the fatty alcohol preferably includes one or more of fatty monohydric alcohols, fatty dihydric alcohols, fatty trihydric alcohols and fatty tetrahydric alcohols, and the fatty monohydric alcohol preferably includes one or more of methanol, ethanol, propanol, butanol, octanol, decanol, undecyl alcohol, dodecanol, tridecanol and tetradecanol, further preferably butanol or octanol, more preferably n-butanol or n-octanol. In the present invention, the fatty dihydric alcohol preferably includes one or more of ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol and neopentyl glycol. In the present invention, the fatty trihydric alcohol preferably includes trimethylolpropane. In the present invention, the fatty tetrahydric alcohol preferably includes pentaerythritol. In the present invention, the ether alcohol substance preferably includes diethylene glycol and / or dipropylene glycol; the ether alcohol substance refers to a substance containing both an ether group and a hydroxyl group.

[0040] The raw materials for preparing the epoxy reactive diluent provided by the present invention include methyl epichlorohydrin. In the present invention, the methyl epichlorohydrin is preferably methyl epichlorohydrin, a byproduct of industrial production of isobutylene. In the present invention, methyl epichlorohydrin is a byproduct of industrial production of isobutylene with abundant output. The present invention uses methyl epichlorohydrin as a raw material to prepare the epoxy reactive diluent, solves the problem of excess methyl epichlorohydrin, an industrial byproduct, and realizes the high added value of the byproduct methyl epichlorohydrin; at the same time, the present invention uses methyl epichlorohydrin as a raw material to expand the variety of epoxy reactive diluents; and, due to the presence of methyl side chains, the synthesized epoxy reactive diluent has a high boiling point, and during use, the volatilization loss is small, the irritation to human skin is small, and the air pollution is small. In addition, the prepared epoxy reactive diluent exhibits relatively good mechanical properties (including tensile strength, elongation at break, flexural strength and impact strength), insulation performance, chemical corrosion resistance and thermal resistance.

[0041] The raw materials for preparing the epoxy reactive diluent provided by the present invention include an inorganic base, and the inorganic base preferably includes sodium hydroxide.

[0042] The raw materials for preparing the epoxy reactive diluent provided by the present invention include a phase transfer catalyst, and the phase transfer catalyst is preferably a quaternary ammonium salt. The quaternary ammonium salt preferably includes one or more of benzyltriethylammonium chloride, benzyltrimethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride and dodecyldimethyl dipolyglycerol ether ammonium chloride, and is specifically preferably benzyltriethylammonium chloride, benzyltrimethylammonium chloride or tetrabutylammonium chloride.

[0043] In the present invention, the molar ratio of the alcohol substance to methyl epichlorohydrin is preferably 1:1-40, more preferably 1:1-20, specifically preferably 1:1, 1:5, 1:7, 1:9, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35 or 1:40.

[0044] In the present invention, the ratio of the total mass of the alcohol substance and methyl epichlorohydrin to the mass of the phase transfer catalyst is preferably 100:0.01-10, more preferably 100:0.1-2, specifically preferably 100:0.01, 100:0.05, 100:0.1, 100:0.5, 100:0.85, 100:0.94, 100:1, 100:1.08, 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8, 100:9 or 100:10.

[0045] In the present invention, the molar ratio of the alcohol substance to the inorganic base is preferably 1:1-10, more preferably 1:2-8, specifically preferably 1:1, 1:1.1, 1:2, 1:2.2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10.

[0046] The present invention also provides a method for preparing the epoxy reactive diluent described in the above technical solution, comprising the following steps:

[0047] The alcohol substance, methyl epichlorohydrin, an inorganic base and a phase transfer catalyst are mixed and reacted to obtain the epoxy active diluent.

[0048] In the present invention, the inorganic alkali is preferably used in the form of an inorganic alkali aqueous solution, and the concentration of the inorganic alkali aqueous solution is preferably 18-48wt%, and specifically preferably 18wt%, 20wt%, 22wt%, 25wt%, 30wt%, 32wt%, 35wt%, 38wt%, 40wt%, 42wt%, 45wt%, 46wt% or 48wt%. In the present invention, the inorganic alkali aqueous solution is preferably added dropwise, and the dropwise addition is preferably completed within 2h.

[0049] In the present invention, the reaction temperature is preferably 20-100°C, more preferably 40-80°C, and specifically preferably 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C or 90°C; the insulation time is preferably 1-24h, more preferably 2-12h, and specifically preferably 2h, 4h, 6h, 12h, 15h, 18h, 21h or 24h. In the present invention, the reaction is preferably carried out under reflux conditions.

[0050] In the present invention, the process of mixing the alcohol substance, methyl epichlorohydrin, an inorganic base and a phase transfer catalyst to react is preferably as follows: at room temperature, the alcohol substance, methyl epichlorohydrin and a phase transfer catalyst are mixed, then the temperature is raised to the reaction temperature, and then an inorganic base solution is added dropwise to react; the reaction time is preferably counted from the time when the addition of the inorganic base solution is completed.

[0051] After the reaction, the present invention preferably further comprises filtering the obtained reaction liquid, washing the obtained filter residue, and then distilling under reduced pressure to obtain the epoxy reactive diluent. In the present invention, the washing reagent is preferably water, and the water is preferably deionized water. The present invention does not specifically limit the parameters of the reduced pressure distillation, as long as the excess methyl epichlorohydrin can be distilled off.

[0052] The present invention also provides the epoxy reactive diluent described in the above technical solution or the use of the epoxy reactive diluent described in the above technical solution in epoxy resin materials.

[0053] In the present invention, the epoxy reactive diluent is applied to the epoxy resin, and can be used as a diluent and also as a modifier to modify the epoxy resin.

[0054] The present invention also provides an epoxy resin material, comprising the following preparation raw materials: epoxy resin, active diluent and curing agent;

[0055] The active diluent is the epoxy active diluent described in the above technical solution and is prepared by the preparation method described in the above technical solution.

[0056] The epoxy resin material provided by the present invention comprises a raw material epoxy resin, wherein the epoxy resin preferably comprises bisphenol A epoxy resin, and the bisphenol A epoxy resin preferably comprises E-51 epoxy resin.

[0057] The epoxy resin material provided by the present invention includes a raw material active diluent, and the active diluent is the epoxy active diluent described in the above technical solution or the epoxy active diluent prepared by the preparation method described in the above technical solution. In the present invention, the addition amount of the epoxy active diluent is preferably 5-20% of the mass of the epoxy resin, and specifically preferably 5%, 10%, 15% or 20%.

[0058] The epoxy resin material provided by the present invention includes a raw material curing agent, and the curing agent preferably includes diethylenetriamine. The present invention does not specifically limit the amount of the curing agent, and those skilled in the art can set it according to actual needs.

[0059] In the present invention, the amount of the curing agent is preferably referred to the book "Curing Agent" published by Chemical Industry Press. Taking diethylenetriamine as the curing agent as an example, the amount calculation formula is as follows:

[0060]

[0061] In the formula: G-the number of grams of curing agent required to cure 100g of epoxy resin, g; M-the relative molecular mass of the curing agent, g / mol; E-the epoxy value of the epoxy resin, mol / 100g; Hn-the total number of active hydrogens in the curing agent molecule.

[0062] The epoxy resin material provided by the present invention preferably also includes a raw material preparation auxiliary agent. The present invention does not specifically limit the type and content of the auxiliary agent, and the auxiliary agent and addition amount familiar to those skilled in the art can be used.

[0063] In the present invention, the preparation method of the epoxy resin material preferably comprises the following steps:

[0064] After the epoxy reactive diluent, epoxy resin and curing agent are mixed, curing and aging are carried out in sequence.

[0065] In the present invention, the mixing method is preferably stirring, and the present invention has no special requirements for the stirring, and the raw materials can be mixed uniformly. In the present invention, the curing time and temperature are preferably determined according to the curing kinetics of the epoxy resin and the curing agent. The present invention has no special requirements for the aging, and the aging operation commonly used in the art can be used.

[0066] The epoxy reactive diluent provided by the present invention, its preparation method and application, and epoxy resin material are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0067] The raw materials n-butanol, n-octanol and neopentyl glycol used in the present invention are of reagent grade and purchased from Shanghai McLean Biochemical Technology Co., Ltd.; methyl epichlorohydrin is of industrial grade and purchased from Shandong Binhua Group Co., Ltd.; sodium hydroxide, tetrabutylammonium chloride, benzyltrimethylammonium chloride and benzyltriethylammonium chloride are of industrial grade and purchased from Anhui Xinyuan Technology Co., Ltd.

[0068] The epoxy value of the aliphatic (β-methyl) glycidyl ether product of the present invention is tested by the hydrochloric acid-acetone method.

[0069] Example 1

[0070] 44.5 g of n-butanol, 319.7 g of methyl epichlorohydrin and 3.1 g of benzyltriethylammonium chloride were added into a four-necked flask equipped with a mechanical stirrer with a mechanical seal, a reflux condenser and a thermometer, and the temperature was raised to 50°C. 82.5 g of a 32 wt% sodium hydroxide solution was added dropwise at 50-55°C within 2 h, and the mixture was kept warm for reaction for 12 h. The obtained reaction liquid was filtered, washed, and the excess methyl epichlorohydrin was recovered by reduced pressure distillation to obtain 58.2 g of butyl-β-methyl glycidyl ether with an epoxide value of 0.4547 mol / 100 g.

[0071] Example 2

[0072] 52.1 g of n-octanol, 298.3 g of methyl epichlorohydrin and 3.8 g of benzyltrimethylammonium chloride were added into a four-necked flask equipped with a mechanical stirrer with a mechanical seal, a reflux condenser and a thermometer, and the temperature was raised to 60°C. 55.0 g of a 32 wt% sodium hydroxide solution was added dropwise at 60-65°C within 2 h, and the mixture was kept warm for reaction for 12 h. The obtained reaction liquid was filtered, washed, and the excess methyl epichlorohydrin was recovered by reduced pressure distillation to obtain 57.6 g of octyl-β-methyl glycidyl ether with an epoxide value of 0.3132 mol / 100 g.

[0073] Example 3

[0074] 41.7 g of neopentyl glycol, 383.6 g of methyl epichlorohydrin and 4.0 g of tetrabutylammonium chloride were added into a four-necked flask equipped with a mechanical stirrer with a mechanical seal, a reflux condenser and a thermometer, and the temperature was raised to 70° C. 110.0 g of a 32 wt% sodium hydroxide solution was added dropwise at 70-75° C. within 2 h, and the mixture was kept warm for reaction for 12 h; the obtained reaction liquid was filtered, washed, and the excess methyl epichlorohydrin was recovered by reduced pressure distillation to obtain 32.1 g of neopentyl glycol di(β-methyl) glycidyl ether with an epoxide value of 0.5358 mol / 100 g.

[0075] The neopentyl glycol di(β-methyl) glycidyl ether prepared in Example 3 was subjected to infrared spectroscopy detection. The results are as follows: Figure 1 shown. Figure 1is the infrared spectrum of the obtained neopentyl glycol di(β-methyl)glycidyl ether, from Figure 1 It can be seen that 1101cm -1 COC asymmetric stretching vibration peak, 912 cm -1 is the characteristic peak of the epoxy group, which shows that the present invention successfully prepares neopentyl glycol di(β-methyl) glycidyl ether.

[0076] According to the addition amount of active diluent of 0%, 5%, 15% and 20% of the mass of E-51 epoxy resin, the neopentyl glycol di(β-methyl)glycidyl ether obtained in Example 3 and E-51 epoxy resin were mixed, and the viscosity change of the obtained epoxy resin system was measured. The results are as follows: Figure 2 As shown. Figure 2 It can be seen that with the addition of epoxy reactive diluent, the viscosity of the epoxy resin system is greatly reduced, indicating that the addition of neopentyl glycol di(β-methyl) glycidyl ether can reduce the viscosity of the epoxy resin.

[0077] Comparative Example 1

[0078] 22.2 g of n-butanol, 83.3 g of epichlorohydrin and 0.4 g of benzyltriethylammonium chloride were added into a four-necked flask equipped with a mechanical stirrer with a mechanical seal, a reflux condenser and a thermometer, and the temperature was raised to 45°C. 41.3 g of a 32 wt% sodium hydroxide solution was added dropwise at 45-50°C within 1 hour, and the reaction was kept warm for 6 hours. The obtained reaction liquid was filtered, washed, and the excess epichlorohydrin was recovered by reduced pressure distillation to obtain 35.3 g of butyl glycidyl ether with an epoxide value of 0.6709 mol / 100g.

[0079] Comparative Example 2

[0080] 52.0 g of n-octanol, 185.0 g of epichlorohydrin and 1.2 g of benzyltriethylammonium chloride were added into a four-necked flask equipped with a mechanical stirrer with a mechanical seal, a reflux condenser and a thermometer, and the temperature was raised to 50° C. 52.5 g of a 32 wt% sodium hydroxide solution was added dropwise at 50-55° C. within 1 h, and the mixture was kept warm for reaction for 6 h. The obtained reaction liquid was filtered, washed, and the excess epichlorohydrin was recovered by reduced pressure distillation to obtain 64.2 g of octyl glycidyl ether with an epoxide value of 0.4082 mol / 100 g.

[0081] Comparative Example 3

[0082] 41.6 g of neopentyl glycol, 296.0 g of epichlorohydrin and 2.2 g of benzyltriethylammonium chloride were added into a four-necked flask equipped with a mechanical stirrer with a mechanical seal, a reflux condenser and a thermometer, and the temperature was raised to 60° C. 110.0 g of a 32 wt% sodium hydroxide solution was added dropwise at 60-65° C. within 1 h, and the mixture was kept warm for reaction for 8 h; the obtained reaction liquid was filtered, washed, and the excess epichlorohydrin was recovered by reduced pressure distillation to obtain 92.8 g of neopentyl glycol diglycidyl ether with an epoxide value of 0.7069 mol / 100 g.

[0083] Application Example 1

[0084] Take 50g of E-51 epoxy resin, add 5.5g of diethylenetriamine curing agent, stir evenly, cure at room temperature for 12h, cure at 80°C for 3h, and age at room temperature for 7 days to obtain epoxy resin cured product.

[0085] Application Example 2

[0086] 2 g of neopentyl glycol di(β-methyl)glycidyl ether prepared in Example 3 was added to 40 g of E-51 epoxy resin, and 4.5 g of diethylenetriamine curing agent was added. After stirring evenly, the mixture was cured at room temperature for 12 h, cured at 80°C for 3 h, and aged at room temperature for 7 days to obtain a cured epoxy resin.

[0087] Application Example 3

[0088] 4 g of neopentyl glycol di(β-methyl)glycidyl ether prepared in Example 3 was added to 40 g of E-51 epoxy resin, and 4.7 g of diethylenetriamine curing agent was added. After stirring evenly, the mixture was cured at room temperature for 12 h, cured at 80°C for 3 h, and aged at room temperature for 7 days to obtain a cured epoxy resin.

[0089] Application Example 4

[0090] 6 g of neopentyl glycol di(β-methyl)glycidyl ether prepared in Example 3 was added to 40 g of E-51 epoxy resin, and 4.9 g of diethylenetriamine curing agent was added. After stirring evenly, the mixture was cured at room temperature for 12 h, cured at 80°C for 3 h, and aged at room temperature for 7 days to obtain a cured epoxy resin.

[0091] Application Example 5

[0092] 8 g of neopentyl glycol di(β-methyl)glycidyl ether prepared in Example 3 was added to 40 g of E-51 epoxy resin, and 5.1 g of diethylenetriamine curing agent was added. After stirring evenly, the mixture was cured at room temperature for 12 h, cured at 80°C for 3 h, and aged at room temperature for 7 days to obtain a cured epoxy resin.

[0093] Application Example 6

[0094] 6 g of butyl-β-methyl glycidyl ether prepared in Example 1 was added to 40 g of E-51 epoxy resin, and 4.9 g of diethylenetriamine curing agent was added. After stirring evenly, the mixture was cured at room temperature for 12 h, cured at 80°C for 3 h, and aged at room temperature for 7 days to obtain a cured epoxy resin.

[0095] Application Example 7

[0096] 6 g of octyl-β-methyl glycidyl ether prepared in Example 2 was added to 40 g of E-51 epoxy resin, and 4.9 g of diethylenetriamine curing agent was added. After stirring evenly, the mixture was cured at room temperature for 12 h, cured at 80°C for 3 h, and aged at room temperature for 7 days to obtain a cured epoxy resin.

[0097] Application Comparative Example 1

[0098] 6 g of butyl glycidyl ether prepared in Comparative Example 1 was added to 40 g of E-51 epoxy resin, and 4.9 g of diethylenetriamine curing agent was added. After stirring evenly, the mixture was cured at room temperature for 12 h, cured at 80°C for 3 h, and aged at room temperature for 7 days to obtain a cured epoxy resin.

[0099] Application Comparative Example 2

[0100] 6 g of octyl glycidyl ether prepared in Comparative Example 2 was added to 40 g of E-51 epoxy resin, and 4.9 g of diethylenetriamine curing agent was added. After stirring evenly, the mixture was cured at room temperature for 12 h, cured at 80°C for 3 h, and aged at room temperature for 7 days to obtain a cured epoxy resin.

[0101] Application Comparative Example 3

[0102] 6 g of neopentyl glycol diglycidyl ether prepared in Comparative Example 3 was added to 40 g of E-51 epoxy resin, and 4.9 g of diethylenetriamine curing agent was added. After stirring evenly, the mixture was cured at room temperature for 12 h, cured at 80°C for 3 h, and aged at room temperature for 7 days to obtain a cured epoxy resin.

[0103] The performance of the epoxy resin cured products prepared using Examples 1 to 7 and Comparative Examples 1 to 3 corresponding to GB / T 2567-2021 was tested, and the results are shown in Table 1.

[0104] Table 1 Mechanical properties of epoxy resin cured products prepared in the application examples and comparative examples of the present invention

[0105]

[0106] According to Table 1, as the amount of epoxy reactive diluent added increases, the epoxy resin cured product has obvious improvements in bending resistance, impact resistance, etc. When the amount of application example 4 of the present invention added is 15% (i.e., the mass of the epoxy reactive diluent is 15% of the mass of the epoxy resin), the elongation at break of the obtained epoxy resin cured product specimen is 31.43% higher than that of pure E-51 (corresponding to application example 1), and the impact strength is 17.19 KJ / m 2 , which is 56.84% higher than that of pure E-51 (corresponding to Application Example 1); in addition, the tensile strength and flexural strength of the cured product are also slightly improved.

[0107] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. An epoxy reactive diluent, characterized in that: The preparation includes the following raw materials: Alcohols, methyl epichlorohydrin, inorganic bases and phase transfer catalysts; The alcohol substance has 1 to 14 carbon atoms; The alcohol substance includes one or more of fatty alcohol and ether alcohol substances.

2. The epoxy reactive diluent according to claim 1, characterized in that The fatty alcohol includes one or more of fatty monohydric alcohol, fatty dihydric alcohol, fatty trihydric alcohol and fatty tetrahydric alcohol; The fatty monohydric alcohol includes one or more of methanol, ethanol, propanol, butanol, octanol, decanol, undecanol, dodecanol, tridecanol and tetradecanol; The fatty diol includes one or more of ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol and neopentyl glycol; The fatty triol includes trimethylolpropane; The fatty tetraol includes pentaerythritol; The ether alcohol substances include diethylene glycol and / or dipropylene glycol.

3. The epoxy reactive diluent according to claim 1, characterized in that: The phase transfer catalyst is a quaternary ammonium salt; the quaternary ammonium salt includes one or more of benzyltriethylammonium chloride, benzyltrimethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride and dodecyldimethyl dipolyglycerol ether ammonium chloride.

4. The epoxy reactive diluent according to claim 1, characterized in that The inorganic base includes sodium hydroxide.

5. The epoxy reactive diluent according to claim 1, characterized in that: The molar ratio of the alcohol substance to methyl epichlorohydrin is 1:1 to 40; The ratio of the total mass of the alcohol substance and methyl epichlorohydrin to the mass of the phase transfer catalyst is 100:0.01-10; The molar ratio of the alcohol substance to the inorganic base is 1:1-10.

6. The method for preparing the epoxy reactive diluent according to any one of claims 1 to 5, characterized in that: The following steps are involved: The alcohol substance, methyl epichlorohydrin, an inorganic base and a phase transfer catalyst are mixed and reacted to obtain the epoxy active diluent.

7. The preparation method according to claim 6, characterized in that: The reaction temperature is 20-100° C., and the insulation time is 1-24 hours.

8. Use of the epoxy reactive diluent according to any one of claims 1 to 5 or the epoxy reactive diluent prepared by the preparation method according to any one of claims 6 to 7 in epoxy resin materials.

9. An epoxy resin material, characterized in that: The preparation method comprises the following raw materials: epoxy resin, active diluent and curing agent; The active diluent is the epoxy active diluent described in any one of claims 1 to 5 or the epoxy active diluent prepared by the preparation method described in any one of claims 6 to 7.

10. The epoxy resin material according to claim 9, characterized in that: The amount of the epoxy reactive diluent added is 5 to 20% of the mass of the epoxy resin; The epoxy resin includes bisphenol A epoxy resin; The curing agent includes diethylenetriamine.

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